CN102694152A - Cathode active material and preparation method and lithium ion battery thereof - Google Patents
Cathode active material and preparation method and lithium ion battery thereof Download PDFInfo
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Abstract
The invention provides a cathode active material which has a core shell structure; the core shell structure comprises an inner core and an outer shell, and the inner core is graphite; wherein the outer shell is composite particles, and comprises a first shell layer and a second shell layer; the first shell layer is tin or tin alloy, and is coated on the surface of the inner core; the second shell layer is alumina, and is coated on the surface of the tin or tin alloy. The invention also provides a preparation method of the cathode active material and a lithium ion battery containing the cathode active material. The lithium ion battery provided by the invention has good charge and discharge performance and cycle performance.
Description
Technical field
The invention belongs to the lithium ion battery field, relate in particular to a kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery.
Background technology
Lithium ion battery has advantages such as voltage height, specific energy is big, security performance is good.At present the negative active core-shell material of commercialization lithium ion battery mainly is a graphite, and in the doff lithium process, the change in volume of graphite is little so have a better cycle performance.Graphite passes through LiC
6The reversible storage of compound Li
+, its Theoretical Mass specific capacity has only 372 mAh/g.Compare with graphite cathode, the tin base cathode active material has higher specific capacity, such as the theoretical capacity of metallic tin up to 994mAh/g.But metallic tin produces the change in volume more than 3 times in charge and discharge process, is prone to cause that electrode peels off, efflorescence and cause capacity seriously to be decayed, and reduces cyclicity greatly.
In order to improve the cyclicity of battery, combine the advantage of the high power capacity of graphite stability and good cycle, tin in the prior art, graphite and tin are made composite material.Compound negative material of a kind of tin-graphite of lithium ion battery and preparation method thereof is for example disclosed among the CN101740764A; This composite material has nucleocapsid structure; Be made up of kernel and shell, kernel is a graphite, and shell is the even complex of metallic tin and amorphous carbon.But the tinbase compound particle is reunited in the process of coated graphite easily, and in the tin-graphite composite material that causes obtaining, tin disperses inhomogeneous, reduces the cycle performance of negative active core-shell material; In addition; Tin is coated on graphite surface, causes tin directly to contact with electrolyte, and electrolyte constantly is decomposed in charge and discharge process; Can reduce the cycle performance and the efficiency for charge-discharge of battery, therefore big limitations the application of tin-graphite composite material as negative material.
Summary of the invention
The invention solves in the negative active core-shell material that exists in the prior art tin and disperse inhomogeneous and be easy to and the electrolyte reaction, cause the relatively poor technical problem of battery efficiency and cycle performance at graphite surface.
The invention provides a kind of negative active core-shell material, this negative active core-shell material has nucleocapsid structure, and said nucleocapsid structure is made up of kernel and shell, and kernel is a graphite; Wherein, shell is a compound particle, comprises ground floor shell and second layer shell; The ground floor shell is tin or ashbury metal, is coated on core surface; Second layer shell is an aluminium oxide, is coated on the outer surface of tin or ashbury metal.
The present invention also provides the preparation method of said negative active core-shell material, may further comprise the steps:
1) graphite is carried out surface treatment;
2) graphite after the surface treatment is mixed with water soluble aluminum compound, add aqueous metal salt again, obtain mixed system; Contain water-soluble pink salt in the said aqueous metal salt, selectivity contains water-soluble M salt; M is not for having the metallic element of electro-chemical activity;
3) toward step 2) mixed system in add the water-soluble alkaline material, to deposition fully, drying obtains presoma;
4) presoma is carried out sintering, obtain said negative active core-shell material.
At last; The invention provides a kind of lithium ion battery; Comprise positive pole, negative pole and be arranged at the barrier film between positive pole, the negative pole; Said negative pole comprises negative electrode collector and is coated on the negative active core-shell material on the negative electrode collector, it is characterized in that, said negative active core-shell material is a negative active core-shell material provided by the invention.
In the negative active core-shell material provided by the invention; Through coating one deck aluminium oxide at tin or ashbury metal surface; Can effectively prevent self reuniting of tin or ashbury metal on the one hand, thereby raising tin or ashbury metal guarantee the cycle performance of negative active core-shell material at the graphite surface dispersing uniformity; On the other hand, alumina-coated prevents that in tin or ashbury metal surface tin or ashbury metal from directly contacting with electrolyte, can effectively reduce electrolyte and be decomposed, and improves the efficiency for charge-discharge and the cycle performance of battery.
Description of drawings
Fig. 1 is the structural representation of negative active core-shell material provided by the invention.
Fig. 2 is that the enlargement ratio of negative active core-shell material B1 is 1000 times SEM figure.
Fig. 3 is that the enlargement ratio of negative active core-shell material B1 is 10000 times SEM figure.
Fig. 4 is that the enlargement ratio of negative active core-shell material B2 is 500 times SEM figure.
Fig. 5 is that the enlargement ratio of negative active core-shell material B2 is 10000 times SEM figure.
Fig. 6 is the EDS figure of negative active core-shell material B1.
Fig. 7 is the EDS figure of negative active core-shell material B2.
Fig. 8 is the XRD figure of negative active core-shell material B2.
Embodiment
The invention provides a kind of negative active core-shell material, as shown in Figure 1, this negative active core-shell material has nucleocapsid structure, and said nucleocapsid structure is made up of kernel 1 and shell 2, and kernel 1 is a graphite; Wherein, shell 2 is a compound particle, comprises ground floor shell 22 and second layer shell 21; Ground floor shell 22 is tin or ashbury metal, is coated on kernel 1 surface; Second layer shell 21 is an aluminium oxide, is coated on the outer surface of tin or ashbury metal.
Negative active core-shell material provided by the invention has nucleocapsid structure, is made up of kernel and shell; Kernel is a graphite, and the ground floor shell that is coated on core surface is tin or ashbury metal, therefore can have graphite material stability and cyclicity preferably concurrently, and the advantage of the high power capacity of tin or ashbury metal.In addition; Among the present invention; The skin of said ground floor shell (being tin or ashbury metal) also is coated with second layer shell; Be aluminium oxide: can prevent effectively that on the one hand tin or ashbury metal from self taking place to the graphite surface process and reunite coating, thereby improve tin or ashbury metal dispersing uniformity, guarantee the cycle performance of negative active core-shell material at graphite surface; On the other hand, alumina-coated prevents that in tin or ashbury metal surface tin or ashbury metal from directly contacting with electrolyte, can effectively reduce electrolyte and be decomposed; The battery that adopts this negative active core-shell material is in discharge process; Can form stable SEI film, the lithium ion embedding take off or tin or ashbury metal expansion process in, the SEI film can not break; Do not need electrolyte decomposition reparation yet, therefore can effectively improve the cycle performance and the efficiency for charge-discharge of battery.
Among the present invention, the particle diameter and the kind of the graphite of kernel there is not particular determination.For example, said graphite can be selected from natural spherical plumbago, natural flake graphite or all kinds of Delanium.The average grain diameter of said graphite is the 2-15 micron, is preferably the 5-12 micron.
Among the present invention, the shell that is coated on graphite surface is a compound particle, comprises ground floor shell and second layer shell; Wherein, the aluminium oxide particles that is used as second layer shell as the outer surface of the tin of ground floor shell or ashbury metal particle coats.Among the present invention, the particle diameter of said shell is the particle diameter of compound particle.Under the preferable case, the particle diameter of said shell is a nanoscale, and therefore outer shell particles has very high electro-chemical activity, has improved gram specific capacity and high rate performance.More preferably under the situation, the average grain diameter of shell is the 10-200 nanometer, more preferably the 10-50 nanometer.
In the negative active core-shell material of the present invention, the content of shell is unsuitable too high, otherwise can reduce the cycle performance of battery.Under the preferable case,, be benchmark with the gross mass of negative active core-shell material, the content＜100wt% of 70wt%≤kernel, the content≤30wt% of 0＜shell.More preferably under the situation, be benchmark with the gross mass of negative active core-shell material, the content of kernel is 75-90wt%, and the content of shell is 10-25wt%.
Said shell comprises ground floor shell and second layer shell, and the ground floor shell is tin or ashbury metal, and higher battery capacity can be provided, and second layer shell is an aluminium oxide, is used to the decomposition that improves the uniformly dispersed of tin or ashbury metal and prevent electrolyte.Content as the aluminium oxide of second layer shell material is unsuitable too high, otherwise can reduce the capacity of battery; In addition,, can all coat tin or ashbury metal outer surface, cause the gram specific capacity of negative electrode active material to descend if alumina content is too high.Simultaneously, the content of aluminium oxide also should not be low excessively, otherwise its influence to tin or ashbury metal reunion is less, is difficult to guarantee the even dispersion of tin or ashbury metal.Under the preferable case, among the present invention, be benchmark with the gross mass of shell, the content＜100wt% of 80wt%≤ground floor shell, the content of 0＜second layer shell is≤20wt%.
Among the present invention, be tin or ashbury metal as the material of ground floor shell.Under the preferable case, the ground floor shell is an ashbury metal.Contain metallic tin and metal M in the said ashbury metal, M is not for having the metallic element of electro-chemical activity.In this ashbury metal, be skeleton, can effectively prevent the battery efflorescence that the tin volumetric expansion causes in discharging and recharging, stop alloy particle to be assembled, thereby guarantee the high power capacity and the cycle life of negative active core-shell material with the metal M; In addition, M can also improve the tin heat treatment temperature, thereby improves the heat treatment temperature of negative active core-shell material, and tin is reunited when avoiding high-temperature fusion.Under the preferable case, M is selected from Co, Ni, Cu, at least a among the Cr.In the ashbury metal, the content of metal M is unsuitable too high, otherwise can reduce capacity.Under the preferable case, in the said ashbury metal, the mol ratio of metallic tin and metal M is 2:1-3.
The present invention also provides the preparation method of said negative active core-shell material, may further comprise the steps:
1) graphite is carried out surface treatment;
2) graphite after the surface treatment is mixed with water soluble aluminum compound, add aqueous metal salt again, obtain mixed system; Contain water-soluble pink salt in the said aqueous metal salt, selectivity contains water-soluble M salt; M is not for having the metallic element of electro-chemical activity;
3) toward step 2) mixed system in add the water-soluble alkaline material, to deposition fully, drying obtains presoma;
4) presoma is carried out sintering, obtain said negative active core-shell material.
According to the method for the invention, said graphite is carried out surface treatment is conventionally known to one of skill in the art, is about to graphite and immerses in acid or the alkali and carry out acidifying or alkalization.Acidifying or basification, one side is removed the not affinity groups of graphite surface, and for example the hydrophilic and oleophobic base improves the evenness of graphite surface on the other hand, thereby can improve the adhesive force of stannic hydroxide and graphite.The temperature of acidifying or alkalization is 60-80 ℃, and the time of acidifying or alkalization is 2-4h.The acid that said acidifying is adopted can be selected from any one in hydrochloric acid, sulfuric acid, the nitric acid.The alkali that said alkalization is adopted is selected from any one in NaOH, potassium hydroxide, the lithium hydroxide.
As those skilled in the art's common practise, graphite is carried out the surface comprise that also acidifying or alkalization accomplish that the back is cleaned, the step of drying.After acidifying or alkalization are accomplished, filter with deionized water wash earlier, washing to graphite pH value is 7 to get final product.Drying can adopt various drying mode of the prior art, and for example air is dry, air-dry or baking is dry, and the present invention does not have particular restriction.
Based on preparation method provided by the invention, surface treatment mixes graphite after accomplishing with water soluble aluminum compound, add aqueous metal salt again.Wherein, contain water-soluble pink salt in the aqueous metal salt, selectivity contains water-soluble M salt; M is not for having the metallic element of electro-chemical activity.Among the present invention, aqueous metal salt is used to form said ground floor shell, promptly forms said tin or ashbury metal; Water soluble aluminum compound is used to form said second layer shell, promptly is coated on the aluminium oxide on tin or ashbury metal surface.
Wherein, the various water soluble aluminum compound that said water soluble aluminum compound can adopt those skilled in the art to use always for example can be selected from AlCl
3, Al
2(SO
4)
3Or Al (NO
3)
3Said water-soluble pink salt is selected from SnCl
4, Sn (SO
4)
2, Sn (NO
3)
4, SnCl
2, SnSO
4, Sn (NO
3)
2Water-soluble M salt is selected from chloride, sulfate or the nitrate of M.Under the preferable case, M is selected from Co, Ni, Cu, Fe, at least a among the Cr.
Among the present invention, the consumption of water soluble aluminum compound is according to the content decision of aluminium oxide in formation negative active core-shell material; The consumption of aqueous metal salt is according to the content decision of tin or ashbury metal in formation negative active core-shell material.Under the preferable case, be benchmark with the graphite of 100 weight portions, the consumption of 0＜water soluble aluminum compound≤5 weight portions, the consumption of 0＜aqueous metal salt≤25 weight portions.More preferably under the situation, in the said aqueous metal salt, the mol ratio of water-soluble pink salt and water-soluble M salt is 2:1-3.
As one embodiment of the present invention, also comprise toward step 2) mixed system in add the step of dispersant.Said dispersant is used for improving mixed system graphite, Al
3+, Sn
4+Or the dispersing uniformity of M ion, prevent tin or ashbury metal generation self reunion in the follow-up sintering on the one hand; On the other hand, improve the absorption affinity between aluminium hydroxide and the stannic hydroxide, and the absorption affinity between graphite and the stannic hydroxide, can form behind alumina-coated tin or the ashbury metal again integral coating behind the sintering in the nucleocapsid structure of graphite surface.Said dispersant be selected among glucose, sucrose, polyvinyl alcohol, citric acid, tartaric acid or the EDTA any one or multiple.Graphite with 100 weight portions is benchmark, the consumption of 0＜dispersant≤10 weight portions.
Preparation in accordance with the present invention is toward step 2) mixed system in add the water-soluble alkaline material, to deposition fully, drying obtains presoma.After adding the water-soluble alkaline material, water soluble aluminum compound, water-soluble pink salt and water-soluble M salt can form the corresponding metal deposition respectively, and said precipitated metal is precipitation of hydroxide or hydroxyl anion salt deposition.In the precipitated metal that forms, contain hydroxyl, and the graphite surface after the surface treatment also has hydroxyl, therefore the hydroxyl bonding can take place.And in precipitation process, Sn
4+, the M ion is that 3-5 can generate corresponding precipitated metal at pH, and Al
3+Need treat that pH is higher than 5 and could forms the metallic aluminium deposition, so graphite surface is preferentially coated by the precipitated metal of tin and M formation, along with the continuation adding of water-soluble alkaline material, the pH value raises gradually in the system, Al
3+Just can be converted into metallic aluminium deposition and be coated on tin surperficial, can obtain said presoma with the precipitated metal that M takes the lead in forming.Baking temperature is 80-100 ℃, and be 1-5h drying time.Dry run is mainly used in the water of removing in the mixed system.
The water-soluble alkaline material that is adopted identical alkali in the time of can adopting and alkalize with graphite for example can be selected from NaOH, potassium hydroxide or lithium hydroxide; Also can adopt other various alkaline matters commonly used that are alkalescence after water-soluble, for example can be selected from sodium carbonate, potash, sodium acid carbonate, saleratus, carbonic hydroammonium.When directly adopting hydroxide such as NaOH, potassium hydroxide or lithium hydroxide that mixed system is precipitated, the precipitated metal that obtains is corresponding precipitate metal hydroxides; If when adopting alkaline matters such as sodium carbonate, sodium acid carbonate that mixed system is precipitated, the precipitated metal that obtains is mainly the hydroxyl carbonate deposition that metal pair is answered.Among the present invention, the consumption of said water-soluble alkaline material is not had particular determination, with metal ion in the reaction system all deposition get final product.
According to the method for the invention, presoma is carried out sintering, can obtain negative active core-shell material provided by the invention.Sintering temperature is 700-1200 ℃, and sintering time is 2-10h.Said sintering can directly carry out in a vacuum, also can in inert atmosphere, carry out, and oxidation reaction takes place when preventing the metallic particles high temperature sintering.Said inert atmosphere is argon gas or nitrogen.
In the sintering process, directly be coated on the tin of graphite surface, decomposition reaction at first takes place in the precipitated metal of M, forms corresponding metal oxide, for example stannic hydroxide is converted into tin oxide, the hydroxide of M is converted into the oxide of M; Sintering temperature continues to raise, and the oxide of tin oxide, M reduces respectively earlier and forms metallic tin, metal M simple substance; Fusion then, metallic tin and metal M interpenetrate, and form the body that dissolves each other of tin and M, and are coated on graphite surface; Temperature continue to raise, and reaches the oxidation Decomposition temperature of metallic aluminium deposition, makes the metallic aluminium deposition pyrolysis that is coated on the surface of dissolving each other generate aluminium oxide, and dissolve each other the relatively density of body of its density is low, therefore is coated on the surface of dissolving each other; Cooling after sintering is accomplished, the body that dissolves each other forms ashbury metal, promptly obtains having the negative active core-shell material of nucleocapsid structure, and kernel is a graphite, and shell is a compound particle, and compound particle comprises ground floor shell and second layer shell; Wherein the ground floor shell is tin or ashbury metal, and it is coated on core surface; Second layer shell is an aluminium oxide, is coated on tin or ashbury metal surface.Among the present invention, sintering temperature should not be lower than 700 ℃, otherwise is difficult to form tin or ashbury metal, and oxide also can't be coated on tin or ashbury metal surface; Sintering temperature also should not be higher than 1200 ℃, otherwise as the particle generation melting recrystallization of shell, the shell particle agglomeration that causes graphite surface to coat, particle diameter become big, reduce battery capacity.
At last; The invention provides a kind of lithium ion battery; Comprise positive pole, negative pole and be arranged at the barrier film between positive pole, the negative pole; Said negative pole comprises negative electrode collector and is coated on the negative active core-shell material on the negative electrode collector that wherein, said negative active utmost point material is negative active core-shell material provided by the invention.
The preparation method of said lithium ion battery can adopt and well known to a person skilled in the art the whole bag of tricks, for example can may further comprise the steps:
(1) preparation positive plate: anode sizing agent is coated on prepares positive plate on the negative electrode collector;
(2) preparation negative plate: the material of negative active core-shell material, conductive agent, binding agent added mixing prepares cathode size in the solvent, after the gained cathode size be coated on prepare positive plate on the negative electrode collector;
(3) encapsulation: with positive plate, barrier film and the negative plate preparation Battery Pole Core that stacks gradually or reel, after be packaged into battery.
Encapsulation of the present invention comprises puts into battery container with Battery Pole Core; Welded cover plate and battery container; In battery container, inject electrolyte, battery is changed into and seals, technology such as change into, seal adopts the various technology that well known to a person skilled in the art, the not special restriction of the present invention.
The not special restriction of the present invention such as positive electrode collector of the present invention, anode sizing agent, negative electrode collector can be adopted to well known to a person skilled in the art various positive electrode collectors, anode sizing agent, negative electrode collector.
To combine specific embodiment that the present invention is done further detailed description below, and should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.The raw material that adopts all is commercially available in embodiment and the Comparative Examples.
(1) be NaOH and the blend of 50g graphite of 50wt% with 200g concentration, be heated to 60 ℃, stir 3h, after washed with de-ionized water is filtered, 60 ℃ of dry 12h, the graphite after obtaining alkalizing;
(2) take by weighing 0.04mol SnSO
4Soluble in water, be made into the aqueous metal salt of 400mL; Graphite after the alkalization is added to and contains 0.01mol/L citric acid and 0.005mol/L AlCl
3The 1L mixed solution in, add aqueous metal salt again, blending and stirring obtains mixed system;
(3) mixed system is carried out water-bath heat temperature raising to 80 ℃, in mixed system, drip 0.1mol/LNH
4HCO
3Solution, constant temperature stirs 2h down for 80 ℃, and is complete to deposition, will precipitate 80 ℃ of following vacuum bakeout 12h after the filtration, obtains precursor samples, is designated as A1;
(4) with precursor samples A1 at 800 ℃ of following vacuum-sintering 10h, obtain the negative active core-shell material sample of present embodiment, be designated as B1.
(5) press mass ratio with negative active core-shell material B1: acetylene black: the mixed of PVDFCMC=80:10:10 is the back compressing tablet evenly, and 120 ℃ of vacuumize 24h obtain the work pole piece; With metal lithium sheet is to electrode, and the celgard2400 polypropylene porous film is a barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1:1) is assembled in being full of the glove box of argon gas for electrolyte, obtains battery sample C1.
Comparative Examples 1
(1) be NaOH and the blend of 50g graphite of 50wt% with 200g concentration, be heated to 60 ℃, stir 3h, after washed with de-ionized water is filtered, 60 ℃ of oven dry 12h, the graphite after obtaining alkalizing;
(2) take by weighing 0.04mol SnSO
4Soluble in water, be made into the aqueous metal salt of 400mL; Graphite after the alkalization is added in the 0.01mol/L citric acid solution of 1L, adds aqueous metal salt again, blending and stirring obtains mixed system;
(3) mixed system is carried out water-bath heat temperature raising to 80 ℃, in mixed system, drip 0.1mol/LNH
4HCO
3Solution, constant temperature stirs 2h down for 80 ℃, and is complete to deposition, will precipitate 80 ℃ of vacuum bakeout 12h after the filtration, obtains precursor samples, is designated as DA1;
(4) with precursor samples DA1 at 800 ℃ of vacuum or sintering 10h, obtain the negative active core-shell material sample of present embodiment, be designated as DB1.
(5) press mass ratio with negative active core-shell material DB1: acetylene black: the mixed of PVDFCMC=80:10:10 is the back compressing tablet evenly, and 120 ℃ of vacuumize 24h obtain the work pole piece; With metal lithium sheet is to electrode, and the celgard2400 polypropylene porous film is a barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1:1) is assembled in being full of the glove box of argon gas for electrolyte, obtains battery sample DC1.
(1) be nitric acid and the blend of 50g graphite of 34wt% with 200g concentration, be heated to 60 ℃, stir 3h, after washed with de-ionized water was filtered, 60 ℃ of oven dry 12h obtained the graphite after the acidifying;
(2) take by weighing 0.04mol SnSO
4With 0.06mol CoCl
3Soluble in water, be made into the aqueous metal salt of 400mL; Graphite after the acidifying is added to contains 0.01mol/L glucose and 0.005mol/LAlCl
3The 1L mixed solution in, add aqueous metal salt again, blending and stirring obtains mixed system;
(3) will carry out water-bath heat temperature raising to 80 ℃ to mixed system, in mixed system, drip 0.1mol/LNH
4HCO
3Solution, constant temperature stirs 2h for 80 ℃, and is complete to deposition, will precipitate 80 ℃ of following vacuum bakeout 12h after the filtration, obtains precursor samples, is designated as A2;
(4) with precursor samples A2 sintering 10h under 800 ℃ of nitrogen atmosphere protections, obtain the negative active core-shell material sample of present embodiment, be designated as B2.
(5) press mass ratio with negative active core-shell material B2: acetylene black: the mixed of PVDFCMC=80:10:10 is the back compressing tablet evenly, and 120 ℃ of vacuumize 24h obtain the work pole piece; With metal lithium sheet is to electrode, and the celgard2400 polypropylene porous film is a barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1:1) is assembled in being full of the glove box of argon gas for electrolyte, obtains battery sample C2.
(1) be nitric acid and the blend of 50g graphite of 34wt% with 200g concentration, be heated to 60 ℃, stir 3h, after washed with de-ionized water was filtered, 60 ℃ of oven dry 12h obtained the graphite after the acidifying;
(2) take by weighing 0.05mol SnSO
4With 0.05mol CoCl
3Soluble in water, be made into the aqueous metal salt of 400mL; Graphite after the acidifying is added to contains 0.01mol/L glucose and 0.005mol/LAlCl
3The 1L mixed solution in, add aqueous metal salt again, blending and stirring obtains mixed system;
(3) will carry out water-bath heat temperature raising to 80 ℃ to mixed system, in mixed system, drip 0.1mol/LNH
4HCO
3Solution, constant temperature stirs 2h for 80 ℃, and is complete to deposition, will precipitate 80 ℃ of following vacuum bakeout 12h after the filtration, obtains precursor samples, is designated as A3;
(4) with precursor samples A3 sintering 10h under 800 ℃ of nitrogen atmosphere protections, obtain the negative active core-shell material sample of present embodiment, be designated as B3.
(5) press mass ratio with negative active core-shell material B3: acetylene black: the mixed of PVDFCMC=80:10:10 is the back compressing tablet evenly, and 120 ℃ of vacuumize 24h obtain the work pole piece; With metal lithium sheet is to electrode, and the celgard2400 polypropylene porous film is a barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1:1) is assembled in being full of the glove box of argon gas for electrolyte, obtains battery sample C3.
Embodiment 4
(1) be nitric acid and the blend of 50g graphite of 34wt% with 200g concentration, be heated to 60 ℃, stir 3h, after washed with de-ionized water was filtered, 70 ℃ of oven dry 12h obtained the graphite after the acidifying;
(2) take by weighing 0.06mol SnSO
4With 0.04mol CoCl
3Soluble in water, be made into the aqueous metal salt of 400mL; Graphite after the acidifying is added to contains 0.01mol/L glucose and 0.008mol/LAlCl
3The 1L mixed solution in, add aqueous metal salt again, blending and stirring obtains mixed system;
(3) will carry out water-bath heat temperature raising to 80 ℃ to mixed system, in mixed system, drip 0.1mol/LNH
4HCO
3Solution, constant temperature stirs 2h for 80 ℃, and is complete to deposition, will precipitate 80 ℃ of following vacuum bakeout 12h after the filtration, obtains precursor samples, is designated as A4;
(4) with precursor samples A4 sintering 10h under 1200 ℃ of nitrogen atmosphere protections, obtain the negative active core-shell material sample of present embodiment, be designated as B4.
(5) press mass ratio with negative active core-shell material B4: acetylene black: the mixed of PVDFCMC=80:10:10 is the back compressing tablet evenly, and 120 ℃ of vacuumize 24h obtain the work pole piece; With metal lithium sheet is to electrode, and the celgard2400 polypropylene porous film is a barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1:1) is assembled in being full of the glove box of argon gas for electrolyte, obtains battery sample C4.
(1) be nitric acid and the blend of 50g graphite of 34wt% with 200g concentration, be heated to 60 ℃, stir 3h, after washed with de-ionized water was filtered, 60 ℃ of oven dry 12h obtained the graphite after the acidifying;
(2) take by weighing 0.08mol SnSO
4With 0.04mol CoCl
3Soluble in water, be made into the aqueous metal salt of 400mL; Graphite after the acidifying is added to contains 0.01mol/L glucose and 0.01mol/LAlCl
3The 1L mixed solution in, add aqueous metal salt again, blending and stirring obtains mixed system;
(3) will carry out water-bath heat temperature raising to 80 ℃ to mixed system, in mixed system, drip 0.1mol/LNH
4HCO
3Solution, constant temperature stirs 2h for 80 ℃, and is complete to deposition, will precipitate 80 ℃ of following vacuum bakeout 12h after the filtration, obtains precursor samples, is designated as A5;
(4) with precursor samples A5 sintering 10h under 800 ℃ of nitrogen atmosphere protections, obtain the negative active core-shell material sample of present embodiment, be designated as B5.
(5) press mass ratio with negative active core-shell material B5: acetylene black: the mixed of PVDFCMC=80:10:10 is the back compressing tablet evenly, and 120 ℃ of vacuumize 24h obtain the work pole piece; With metal lithium sheet is to electrode, and the celgard2400 polypropylene porous film is a barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1:1) is assembled in being full of the glove box of argon gas for electrolyte, obtains battery sample C5.
Comparative Examples 2
(1) be nitric acid and the blend of 50g graphite of 34wt% with 200g concentration, be heated to 60 ℃, stir 3h, after washed with de-ionized water was filtered, 60 ℃ of oven dry 12h obtained the graphite after the acidifying;
(2) take by weighing 0.04mol SnSO
4With 0.06mol CoCl
3Soluble in water, be made into the aqueous metal salt of 400mL; Graphite after the acidifying is added in the 0.01mol/L glucose solution of 1L, add aqueous metal salt again, blending and stirring obtains mixed system;
(3) will carry out water-bath heat temperature raising to 80 ℃ to mixed system, in mixed system, drip 0.1mol/LNH
4HCO
3Solution, constant temperature stirs 2h for 80 ℃, and is complete to deposition, will precipitate 80 ℃ of following vacuum bakeout 12h after the filtration, obtains precursor samples, is designated as DA2;
(4) with precursor samples DA2 sintering 10h under 800 ℃ of nitrogen atmosphere protections, obtain the negative active core-shell material sample of present embodiment, be designated as DB2.
(5) press mass ratio with negative active core-shell material DB2: acetylene black: the mixed of PVDFCMC=80:10:10 is the back compressing tablet evenly, and 120 ℃ of vacuumize 24h obtain the work pole piece; With metal lithium sheet is to electrode, and the celgard2400 polypropylene porous film is a barrier film, 1mol/L LiPF
6Ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1:1) is assembled in being full of the glove box of argon gas for electrolyte, obtains battery sample DC2.
Performance test:
1, sem test
Adopt scanning battery (SEM) anticathode active material B1-B2 to test, obtain Fig. 2-3, Fig. 4-5 respectively.
2, electron spectrum (EDS) test
Adopt scanning electron microscopy energy disperse spectroscopy anticathode active material B1, B2 to detect, obtain Fig. 6 and Fig. 7.
3, X-ray diffraction analysis
Adopt Japanese D/MAX-PC2200 X x ray diffractometer x of science (the Cu target, λ=0.15405nm) anticathode active material B2 carries out the crystal structure analysis of thing phase, correspondence obtains diffracting spectrum Fig. 8.
Can know that by Fig. 2-3 and Fig. 4-5 negative active core-shell material B1 provided by the invention, B2 have nucleocapsid structure.Among Fig. 6, detect big characteristic peak of C, Sn and Al, the more weak characteristic peak of O, explain that kernel is a graphite among the B1, shell is tin and aluminium oxide, and alumina-coated is in the outer surface of tin.Among Fig. 7, detect big characteristic peak of C, Sn, Co and Al, the more weak characteristic peak of O, explain that kernel is a graphite among the B2, shell is tin-cobalt alloy and aluminium oxide, and alumina-coated is at the tin-cobalt alloy outer surface.Diffracting spectrum in conjunction with Fig. 8 can know that the composition of tin-cobalt alloy is Sn
2Co
3There is not Al in the collection of illustrative plates in addition
2O
3Characteristic peak possibly be due to its content is too low or it exists with amorphous state.
4, battery performance test:
Battery sample C1-C3 and DC1-DC2 are carried out following performance test respectively:
(1) charging and discharging capacity:
Battery is set to discharge condition, and discharge current density is 2mA/cm
2, discharge cut-off voltage is 5mV, discharge finishes promptly out of service, calculates first discharge specific capacity.
After discharge finished first, battery was set to charged state again, and the density of charging current is 2mA/cm
2, the charging cut-ff voltage is 2.5V, charging finishes, and calculates the initial charge specific capacity.
(2) cycle performance:
Constant current with 0.2mA carries out constant current charge to battery, and charging is by voltage 2.5V, equally with the constant current of 0.2mA to the battery constant-current discharge; Discharge cut-off voltage is 0.005V; Shelved 10 minutes, and repeated above step, make continuous charge-discharge test; Obtain the battery capacity after battery circulates for 40 times, calculate the discharge capacitance of 40 circulation back batteries.
Test result is as shown in table 1.
Table 1
Can find out that from the test result of table 1 compare with existing graphite material, tin coated graphite composite material, the specific capacity of lithium ion battery provided by the invention significantly improves, in addition, its first charge-discharge efficiency and cycle performance are all better.
Claims (13)
1. negative active core-shell material, this negative active core-shell material has nucleocapsid structure, and said nucleocapsid structure is made up of kernel and shell, and kernel is a graphite; It is characterized in that shell is a compound particle, comprise ground floor shell and second layer shell; The ground floor shell is tin or ashbury metal, is coated on core surface; Second layer shell is an aluminium oxide, is coated on tin or ashbury metal surface.
2. negative active core-shell material according to claim 1 is characterized in that, the average grain diameter of said kernel is the 2-15 micron, and the average grain diameter of shell is the 10-200 nanometer.
3. negative active core-shell material according to claim 1 is characterized in that, is benchmark with the gross mass of negative active core-shell material, the content＜100wt% of 70wt%≤kernel, the content≤30wt% of 0＜shell.
4. according to claim 1 or 3 described negative active core-shell materials, it is characterized in that, is benchmark with the gross mass of shell, the content＜100wt% of 80wt%≤ground floor shell, and the content of 0＜second layer shell is≤20wt%.
5. negative active core-shell material according to claim 1 is characterized in that, contains metallic tin and metal M in the said ashbury metal, and M is not for having the metallic element of electro-chemical activity; In the said ashbury metal, the mol ratio of metallic tin and metal M is 2:1-3.
6. negative active core-shell material according to claim 5 is characterized in that M is selected from Co, Ni, Cu, at least a among the Cr.
7. the preparation method of the described negative active core-shell material of claim 1 may further comprise the steps:
1) graphite is carried out surface treatment;
2) graphite after the surface treatment is mixed with water soluble aluminum compound, add aqueous metal salt again, obtain mixed system; Contain water-soluble pink salt in the said aqueous metal salt, selectivity contains water-soluble M salt; M is not for having the metallic element of electro-chemical activity;
3) toward step 2) mixed system in add the water-soluble alkaline material, to deposition fully, drying obtains presoma;
4) presoma is carried out sintering, obtain said negative active core-shell material.
8. preparation method according to claim 7 is characterized in that, said surface treatment comprises graphite immersed carries out acidifying or alkalization in acid or the alkali, and the temperature of acidifying or alkalization is 60-80 ℃.
9. preparation method according to claim 7 is characterized in that, water soluble aluminum compound is AlCl
3, Al
2(SO
4)
3Or Al (NO
3)
3Water-soluble pink salt is SnCl
4, Sn (SO
4)
2, Sn (NO
3)
4, SnCl
2, SnSO
4, Sn (NO
3)
2Chloride, sulfate or nitrate that water-soluble M salt is M, M is selected from Co, Ni, Cu, at least a among the Cr.
10. preparation method according to claim 7 is characterized in that, is benchmark with the graphite of 100 weight portions, the consumption of 0＜water soluble aluminum compound≤5 weight portions, the consumption of 0＜aqueous metal salt≤25 weight portions.
11. preparation method according to claim 7 is characterized in that step 2) in also comprise the step that adds dispersant in the mixed system; Said dispersant is glucose, sucrose, polyvinyl alcohol, citric acid, tartaric acid or EDTA; Graphite with 100 weight portions is benchmark, the consumption of 0＜dispersant≤10 weight portions.
12. preparation method according to claim 7 is characterized in that, sintering temperature is 700-1200 ℃, and sintering time is 2-10h.
13. lithium ion battery; Comprise positive pole, negative pole and be arranged at the barrier film between positive pole, the negative pole; Said negative pole comprises negative electrode collector and is coated on the negative active core-shell material on the negative electrode collector; It is characterized in that said negative active core-shell material is each described negative active core-shell material of claim 1-6.
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